Abstract
| Language | English |
|---|---|
| Pages | 13747–13751 |
| Number of pages | 5 |
| Journal | Angewandte Chemie International Edition |
| Volume | 56 |
| Issue number | 44 |
| Early online date | 11 Sep 2017 |
| DOIs | |
| Publication status | Published - 2 Oct 2017 |
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Keywords
- electron-transfer reactions
- hydride-transfer pathways
- single-electron transfer
- hydride delivery reactions
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Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH). / Smith, Andrew J.; Young, Allan; Rohrbach, Simon; O'Connor, Erin F.; Allison, Mark; Wang, Hong-Shuang; Poole, Darren L.; Tuttle, Tell; Murphy, John A.
In: Angewandte Chemie International Edition, Vol. 56, No. 44, 02.10.2017, p. 13747–13751.Research output: Contribution to journal › Article
TY - JOUR
T1 - Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)
AU - Smith, Andrew J.
AU - Young, Allan
AU - Rohrbach, Simon
AU - O'Connor, Erin F.
AU - Allison, Mark
AU - Wang, Hong-Shuang
AU - Poole, Darren L.
AU - Tuttle, Tell
AU - Murphy, John A.
PY - 2017/10/2
Y1 - 2017/10/2
N2 - Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes.
AB - Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes.
KW - electron-transfer reactions
KW - hydride-transfer pathways
KW - single-electron transfer
KW - hydride delivery reactions
U2 - 10.1002/anie.201707914
DO - 10.1002/anie.201707914
M3 - Article
VL - 56
SP - 13747
EP - 13751
JO - Angewandte Chemie International Edition
T2 - Angewandte Chemie International Edition
JF - Angewandte Chemie International Edition
SN - 1433-7851
IS - 44
ER -